Alkyl ether of linear methylene nitramines



United States Patent 3,104,262 ALKYL ETHER 0F LINEAR METHYLENENITRAMINES William A. Gey and Robert W. Van Dolah, China Lake, Califl,assignors to the United States of America as represented by theSecretary of the Navy No Drawing. Filed Jan. 27, 1953, Ser. No. 333,623

1 Claim. (Cl. 260-584) (Granted under Title 35, US. Code (1952), sec.266) The invention described herein may be manufactured and used by orfor the Government of the United States of America for governmentalpurposes without the payment of any royalties thereon or therefor.

The invention relates to new chemical compounds, more particularly, itrelates to ethers of linear methylene nitramines of the structurewherein R is selected from the group consisting of hydrogen, alkyl oralkoxy, R is alkoxy and x is an integer.

An objective in the production of high explosives is an explosive whichis relatively insensitive to detonation by mechanical shock and highlysensitive to detonation by explosive shock. A number of explosives whichhave high explosive efiiciency are unsuitable for military or commercialuse because their sensitivity to mechanical shock makes handling of themextremely hazardous. iAn expedient which has been used .to overcome thisdifiiculty in a number of explosive compositions is the incorporationtherein of an additive which reduces the sensitivity of the explosive tomechanical shock. For example, parafiin hydrocarbons have been added tosuch explosives as tetranitromethane; nitro aromatic hydrocarbons havebeen added to blasting gelatine; and celulose acetate has been added tonitroglycerin for the above purpose. A difliculty attendant to theincorporation of additives in explosive compositions is the fact thatordinarily certain desirable qualities such as brisance, density andothers are sacrificed. Accordingly, this procedure ordinarily results ina compromise between various properties of the explosive.

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The additives of this invention which meet the above objects comprisealkyl ethers prepared from NSX(1- nitroxy 2,4,6-trinitro 2,4,6triazaheptane), ATX(1,7- di nitroxy 2,4,6 trinitro 2,4,6 triazaheptane),lnitroxy 2,4,6 trinitro 2,4,6 triazadecane and 1,9 dinitroxy 2,4,6,8tetranitro 2,4,6,8 tetrazanonane. The ethers found most suitable arethose having from four to eight atoms in the alkyl chain. The compoundsare prepared by heating an excess of the appropriate alcohol with NSX,ATX, 1-nitroxy-2,4,6-trinitro-2,4,6-triazadecane,l,9-dinitroxy-2,4,6,8-tetranitro-2,4,6,8-terazanoname, or otherappropriate linear methylene nitramine.

The following specific examples will serve to illustrate the preparationof the compounds of the invention:

Example 1 The butyl ether from NSX was prepared by adding 5 grams of NSXto 20 cc. of n-butyl alcohol and stirring the mixture at 95 C. untilsolution was effected. The solution was poured into an equal volume ofbenzene, cooled at 0 C. for 48 hours and filtered. The product wasrecrystallized from methanol.

The compound has the following structural formula:

The above procedure was repeated to produce the amyl, hexyl and heptylethers from NSX by reacting the appropriate alcohol with NSX with theexception that the mixtures producing these three ethers were heated onehour, one and three-fourths hours and three hours respectively. Theyields of butyl, amyl and heptyl ethers were 5 grams (97%), 4.4 grams(82%), 5.5 grams (97%) and 5.5 grams (94%), respectively.

Example 2 The di-n-octyl ether from ATX was prepared by heating 25 gramsof n-octyl alcohol at 85 C. for 2 hours with 5 grams of ATX to givecomplete solution. The solution was filtered while hot, cooled,refiltered at room temperature and further purified. The compound formedhas the following formula:

Petroleum Waxes have been used in the past as additives to such highexplosives as RDXJ Although these additives reduce the sensitivity ofthe explosive to mechanical shock, they also produce a final compositionwhich is excessively sticky. This latter characteristic makes processingdifficult. In addition, their incorporation in the explosive results ina lowering of its overall density, thus resulting in a less compactexplosive with resultant loss of explosive power.

It is, therefore, an object of this invention to provide additives forexplosives which reduce the sensitivity of the explosive to mechanicalshock without adversely affecting other desirable explosive properties.

It is another object of this invention to provide additives forexplosives which produce a product which is not tacky or sticky.

It is still another object of this invention to provide additives forexplosives which produce a product of increased density.

It is a further object of this invention to provide additives forexplosives which produce a final product having good storage stability.

The above procedure was repeated to produce di-nbutyl, di-n-amyl,di-iso-amyl, di-n-hexyl and di-n-hepty1 ethers from ATX by reacting theappropriate alcohol with ATX.

Example 3 Example 4 The di-n-hexyl ether from1,9-dinitroxy-2,4,6,8-tetra nitro-2,4,6,S-tetrazanonane was prepared asfollows:

15 cc. of 1,9-dinitroxy-2,4,6,8-tetranitro-2,4,6,8-tetrazanonane weremixed with 4 grams of n-hexyl alcohol and the mixture stirred at 120 C.until complete solution and for 20 minutes thereafter. The mixture wascooled at 0 C. for one hour, filtered and the ether recovered byrecrystallization for methanol. 3.9 grams of the ether were obtained,amounting to an 89% yield.

The compound has the following structural formula:

ETHERS FROM 1-NITROXY-2,4,6-TRINITRO-2,4,6-TRIAZA- DECANE methyl. 92-93ETHERS FROM 1,9-DINI'IROXY-2,4,6,8-TEIRANITRO-2,4,6,8- TETRAZANONANE Asdisclosed in the co-pending application of William A. Gey, entitledExplosive Compositions, Serial IIlI IHI'II II-II1EIIITOQIII1TOZIIINHZIIINOQIII HHHHHH H-(IJ-CI(IJCCIJCIIOCNfi3-N(f-N?-0-( J- ('J-( :c l- 1-H H H H H H H H H H H H 1'1 1'1 1'1 III H I!Example 5 No. 333,622, filed in the US. Patent Ofiice January 27, 1953,which has matured into Patent No. 2,982,639, Examples 1 t0 4 Show hgenfil'al methods of P P issued May 2, 1961, the addition of the aboveethers to a the compounds o the invention, the speclfic p p such highexplosives as RDX results in an explosive of i165 0f thfisfi belngglvel'l as follows! improved density and therefore higher explosivepower.

In addition, the presence of these ethers renders the ex- ETHERS FROMNSX plosive less sensitive to mechanical shock. For example, PercentPercent M If such a composition is disclosed in the above applicationnitrogen nmogen it having a ballistic mortar value 138.1% that of TNT, a3 5 3- (d gg s density of 1.661 grams per cc., a heat of explosion of1230 calories per gram and an impact sensitivity close bum 2709 27.77101402 to that of composition A. Further, the addition of the amyll l gg present compounds to explosives does not render them 1'1 hgpijyl 23.8623.96 88.5-89 0 g igz z g ig gg they can be readlly processed The etherof the formula ETHERS FROM A'IX N02 H N02 H NO, H

I l l di-n-butyL .3 HCH2NC--NCNC-O C4118 (li-n-amyl 20 .50 22 .25 82-83l (li-iso-amyl 83.5-85 H H H gfgfigifg' gig; References Cited in thefile of this patent di-n-0ctyl 16- 17-50 80-82 2,381,408 Senkies Aug. 7,1945 2,678,927 Wright et a1. May 18, 1954 45 OTHER REFERENCES Chute eta1.: Canadian Journal of Research, Vol. 27B, pages 503-19 (1949).

